Image transfer material and polymer composition

ABSTRACT

Provided is an image transfer material, comprising a support, optionally at least one barrier layer, a melt transfer layer, and an image receiving layer. Also provided is a process for preparing the image transfer material. Further provided is a heat transfer process using the disclosed material. In the heat transfer process, after imaging, the image receiving layer and melt transfer layer are peeled away from the optionally barrier-coated support material and placed, preferably image side up, on top of a receptor element. A non-stick sheet is then optionally placed over the imaged peeled material and heat is applied to the top of the optional non stick sheet. The melt transfer layer then melts and adheres the image to the receptor element. A composition comprising: at least one self-crosslinking polymer, and at least one dye retention aid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/958,126, filed on Dec. 3, 2015, now patented as U.S. Pat. No.9,718,295, which is a continuation of U.S. patent application Ser. No.14/082,901, filed on Nov. 18, 2013, now patented as U.S. Pat. No.9,227,461, which is a divisional of U.S. patent application Ser. No.13/668,672, filed on Nov. 5, 2012, now patented as U.S. Pat. No.8,613,988, which is a continuation of U.S. patent application Ser. No.13/005,849, filed on Jan. 13, 2011, now patented as U.S. Pat. No.8,334,030, which is a divisional of U.S. patent application Ser. No.10/589,022, filed on Mar. 8, 2007, now abandoned, which is anationalization under 35 U.S.C. § 371 and claims the benefit of priorityunder 35 U.S.C. § 120 to International Patent Application No.PCT/US2005/03866, filed on Feb. 9, 2005, and published on Aug. 25, 2005as WO 2005/077663 A1, which claims priority under 35 U.S.C. § 119(e) toU.S. Provisional Application Ser. No. 60/542,886, filed on Feb. 10,2004, and to U.S. Provisional Application Ser. No. 60/616,650, filed onOct. 8, 2004, all of which are incorporated herein in their entiretiesby this reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to an image transfer material, comprisinga support, optionally at least one barrier layer, a melt transfer layer,and an image receiving layer. The top surface of the image receivinglayer is receptive to images, for instance, ink jet images, photocopyimages, etc. Optionally, one or more opaque layers may be coated betweenthe melt transfer layer and the image receiving layer. The optionalopaque layer(s) adds a rigid or stiff quality to the transfer materialfor ease of handling, as well as having opacity, especially white, toenhance visibility of the image when placed thereon. When optionalopaque layers are placed between the melt transfer layer and the imagereceiving layer, the support and barrier layers are both optional sincethe combination of melt transfer layer, opaque layer(s) and imagereceiving layer may function independently as an image transfer sheet,which may be optionally imaged prior to transfer to a receptor element.For instance, a material comprising the melt transfer layer, one or moreopaque layers and an image receiving layer may be optionally imaged,placed melt transfer layer down on a receptor element, optionally imagedand then adhered using a heat source.

The present invention further relates to a process for preparing theabove image transfer material. According to the present invention,optionally at least one barrier layer is coated on the support, and themelt transfer layer is coated onto the optionally barrier-coatedsupport. Possible ways of applying the melt transfer layer includeextrusion and lamination. Next, the image receiving layer is coated ontothe melt transfer layer.

The present invention further relates to a heat transfer process usingthe same material. For instance, after imaging, the image receivinglayer and melt transfer layer are peeled away from the support materialand placed, preferably image side up, on top of a receptor element, suchas cotton or cotton/polyester blend fabrics or the like. A non-sticksheet is then optionally placed over the imaged peeled material andheat, for instance, from a source such as a hand iron, is applied to thetop of the optional non-stick sheet. If a heat source such as an oven isused, a non-stick sheet is unnecessary. A non-stick sheet is also notnecessary if the material does not stick to the heat source, such as astick-free hand iron or heat press. The melt transfer layer then meltsand adheres the image to the receptor element. After heat application,the non-stick sheet is removed and the image remains attached to thereceptor element.

Description of the Prior Art

Textiles such as shirts (e.g., tee shirts) having a variety of designsthereon have become very popular in recent years. Many shirts are soldwith pre-printed designs to suit the tastes of consumers. In addition,many customized tee shirt stores are now in the business of permittingcustomers to select designs or decals of their choice. Processes havealso been proposed which permit customers to create their own designs ontransfer sheets for application to tee shirts by use of a conventionalhand iron, such as described in U.S. Pat. No. 4,244,358. Furthermore,U.S. Pat. No. 4,773,953, is directed to a method for utilizing apersonal computer, a video camera or the like to create graphics,images, or creative designs on a fabric. These designs may then betransferred to the fabric by way of an ink jet printer, a laser printer,or the like.

Other types of heat transfer sheets are known in the art. For example,U.S. Pat. No. 5,798,179 is directed to a printable heat transfermaterial using a thermoplastic polymer such as a hard acrylic polymer orpoly(vinyl acetate) as a barrier layer, and has a separate film-formingbinder layer. U.S. Pat. No. 5,271,990 relates to an image-receptive heattransfer paper which includes an image-receptive melt-transfer filmlayer comprising a thermoplastic polymer overlaying the top surface of abase sheet. U.S. Pat. No. 5,502,902 relates to a printable materialcomprising a thermoplastic polymer and a film-forming binder. U.S. Pat.No. 5,614,345 relates to a paper for thermal image transfer to flatporous surfaces, which contains an ethylene copolymer or a ethylenecopolymer mixture and a dye-receiving layer.

Other examples of heat transfer materials are disclosed by, for example,U.S. Pat. No. 6,410,200 which relates to a polymeric compositioncomprising an acrylic dispersion, an elastomeric emulsion, aplasticizer, and a water repellant. U.S. Pat. No. 6,358,660 relates to abarrier layer. The barrier layer of U.S. Pat. No. 6,358,660 provides for“cold peel,” “warm peel” and “hot peel” applications and comprisesthermosetting and/or ultraviolet (UV) curable polymers. U.S. applicationSer. No. 09/980,589, filed Dec. 4, 2001, relates to a transferablematerial having a transfer blocking overcoat and to a process using saidheat transferable material having a transfer blocking overcoat.

Some of the above-mentioned applications contain specific systems forforming clear images which are subsequently transferred onto thereceptor element. However, other heat transfer systems exist, forexample, those disclosed by U.S. Pat. Nos. 4,021,591, 4,555,436,4,657,557, 4,914,079, 4,927,709, 4,935,300, 5,322,833, 5,413,841,5,679,461, 5,741,387, and 6,432,514.

Problems with many known transfer sheets is the expense involved incoating numerous solutions onto a support material and the overall feelof the imaged product. However, the present invention represents arevolution in the image transfer industry. It is very inexpensive, has avery soft feel to the touch, and can be washed in the washing machinewith detergent. No special washing or drying procedures are required inorder to preserve the transferred image. Additionally, it includes theadvantages of a “peel-away” imaging material. With a peel-away material,the image that is placed on the imaging material is transferred directlyto the receptor element without need of an inverted or reversed image,such as disclosed in U.S. Pat. No. 6,383,710 B2. Traditional transfermaterials required images to be added to the material in an inverted orreversed orientation so that the image, when placed face down on thereceptor element, would appear in the correct orientation in the finalproduct.

SUMMARY OF THE INVENTION

In order to attract the interest of consumer groups that are alreadycaptivated by the tee shirt rage described above, the present inventionprovides, in one embodiment, an improved transfer sheet. In anotherembodiment, the present invention provides for a process for preparingthe transfer sheet. In another embodiment, the present inventionprovides for a heat transfer of images to a receptor element.

The present invention relates to an image transfer material, comprisinga support, an optional barrier layer, a melt transfer layer, and animage receiving layer. Optionally, one or more opaque layers may becoated between the melt transfer layer and the image receiving layer.

Further, when one or more opaque layer is placed between the melttransfer layer and the image receiving layer, both the support and thebarrier layer are optional since the combination of melt transfer layer,opaque layer(s) and image receiving layer may function as an imagetransfer sheet, which may be optionally imaged prior to transfer to areceptor element. For instance, a material comprising the melt transferlayer, one or more opaque layers and an image receiving layer may beoptionally imaged, placed melt transfer layer down on a receptorelement, optionally imaged and then adhered using a heat source. Thepresent invention further relates to a process for preparing the aboveimage transfer material. According to the present invention, theoptional barrier layer is coated on the support, the transfer layer isapplied onto the optionally barrier-coated support, and the imagereceiving layer is coated onto the laminated transfer layer. Ways ofapplying the melt transfer layer include extrusion and lamination.

The embodiment using one or more opaque layers between a melt transferlayer and an image receiving layer may be prepared by coating the melttransfer layer on one side of the opaque layer(s) and the imagereceiving layer on the other. Alternatively, an optional barrier layeris coated on a support, the melt transfer layer is applied onto theoptionally barrier-coated support, the one or more opaque layers is/areapplied over the melt transfer layer and then and the image receivinglayer is coated onto the melt transfer layer. Then, the support ispeeled away from the upper layers leaving the melt transfer layer, uponwhich is the one or more opaque layers, upon which is the imagereceiving layer.

The present invention further relates to a heat transfer process usingthe present image transfer material. First, the top surface of the imagereceiving layer is optionally imaged using any imaging technique. Next,the optionally imaged, image receiving layer and melt transfer layer arepeeled away from the support. Then the optionally imaged peeled materialis placed, preferably imaged side up (when imaged), on top of a receptorelement and further optionally imaged. Alternatively, the imagereceiving layer and melt transfer layer are first peeled away from thesupport, then optionally imaged, and then placed, preferably imaged sideup (when imaged) on top of the receptor element and further optionallyimaged. Alternatively, when one or more opaque layers are present, themelt transfer layer, with one or more opaque layer(s) and imagereceiving layer are first either peeled from the support and optionallyimaged or optionally imaged and then peeled from the support. Next, heatis applied (e.g., by way of a hand iron, a heat press or an oven), tothe top of the optional image. If a hand iron or a heat press is used, atack-free sheet should be placed between the iron or press and theimaged material, unless the heating device is itself tack-free. Uponheating, the melt transfer layer melts and adheres the optionally imagedimage receiving layer to the receptor element. After heat application,the non-stick sheet is removed and the image remains attached to thereceptor element.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from thedetailed description given hereinbelow, and the accompanying drawingsthat are given by way of illustration only and thus are not limitive ofthe present invention, and wherein:

FIG. 1 is a cross-sectional view of one embodiment of the transferelement of the present invention;

FIG. 2 illustrates the step of ironing the transfer element of thepresent invention onto a tee shirt or the like.

DETAILED DESCRIPTION OF THE INVENTION

In one embodiment, the present invention relates to an image transfermaterial, comprising a support, an optional barrier layer, a melttransfer layer, and an image receiving layer. Optionally, one or moreopaque layers may be coated between the melt transfer layer and theimage receiving layer. When optional opaque layers are placed betweenthe melt transfer layer and the image receiving layer, the support andbarrier layers are both optional.

In another embodiment, the present invention relates to a process forpreparing the above image transfer material. According to the presentinvention, the optional barrier layer is coated on the support, the melttransfer layer is coated onto the optionally barrier-coated support, andthe image receiving layer is coated onto the laminated transfer layer.The melt transfer layer may be coated by extrusion or lamination ontothe optionally barrier-coated support.

In yet another embodiment, the present invention further relates to aheat transfer process using the present image transfer material. First,the top surface of the image receiving layer is optionally imaged usingany conventional imaging technique including but not limited to, ink jetprinters, bubblejet printers, thermal inkjet methods, piezo inkjetmethods, laser printers, crayons, and the like. Next, the optionallyimaged, image receiving layer and melt transfer layer are peeled awayfrom the support (e.g., peeled in the absence of water or other chemicalaid). Then the optionally imaged peeled material is placed, preferablyimaged side up (when imaged), on top of a receptor element andoptionally imaged. Alternatively, the image receiving layer and melttransfer layer are first peeled away from the support, then optionallyimaged, and then placed, preferably imaged side up (when imaged) on topof the receptor element and optionally imaged. Next, heat is applied(e.g., by way of a hand iron, a heat press or an oven), to the top ofthe optional image. If a hand iron or a heat press is used, a tack-freesheet should be placed between the iron or press and the imagedmaterial, unless the heating device is itself tack-free. Upon heating,the melt transfer layer melts and adheres the optionally imaged imagereceiving layer to the receptor element. After heat application, thenon-stick sheet is removed and the image remains attached to thereceptor element.

The present invention also provides for a kit containing the transfersheet of the present invention and instructions for transferring animage thereon. The kit may also optionally contain a tack-free sheet,markers, paint, crayons, tee-shirts, prep-shirts or other design aids.

A. The Transfer Material

1. Support Layer

The support is a thin flexible, but non-elastic carrier sheet. Thesupport is not particularly limited and may be any conventional supportsheet which is suitably flexible. Typically, the support sheet is apaper web, plastic film, metal foil, wood pulp fiber paper, vegetableparchment paper, lithographic printing paper or similar material.

In one embodiment of the present invention an appropriate supportmaterial may include but is not limited to a cellulosic nonwoven web orfilm, such as a smooth surface, heavyweight (approximately 24 lb.) laserprinter or color copier paper stock or laser printer transparency(polyester) film. However, highly porous supports are less preferredbecause they tend to absorb large amounts of any material coatedthereon. The particular support used is not known to be critical, solong as the support has sufficient strength for handling, copying,coating, heat transfer, and other operations associated with the presentinvention. Accordingly, in accordance with some embodiments of thepresent invention, the support may be the base material for anyprintable material, such as described in U.S. Pat. No. 5,271,990. In apreferred embodiment, the support layer is 70-100 GSM paper.

2. Optional Barrier Layer

The support contains an optional barrier coating on one or both supportsurfaces. Any suitable barrier layer may be used. For instance, barrierlayers may include, but are not limited to, the barrier layers disclosedin U.S. Pat. Nos. 6,410,200, 6,358,660, 5,501,902, 5,271,990, and5,242,739, which are herein incorporated by reference.

Other suitable barrier layers include those disclosed in U.S. Pat. Nos.4,021,591, 4,555,436, 4,657,557, 4,914,079, 4,927,709, 4,935,300,5,322,833, 5,413,841, 5,679,461, 5,741,387, 5,798,179, and 5,603,966,all of which are herein incorporated by reference.

Lastly, suitable barrier layers include the barrier layers of U.S. Pat.Nos. 4,773,953, 4,980,224, 5,620,548, 5,139,917, 5,236,801, 5,883,790,6,245,710, 6,083,656, 5,948,586, 6,265,128, 6,033,824, 6,294,307,6,410,200 and 6,358,660, and U.S. application Ser. Nos. 09/366,300,09/547,760, 09/637,082, 09/828,134, 09/980,589, 09/453,881, 09/791,755,10/089,446, and 10/205,628, and Provisional U.S. Application Ser. Nos.60/396,632 and 60/304,752.

Coating weights for the barrier layer may range from one (1) gram permeter square to 20 grams per meter square, preferably from 1 g/m.sup.2to 15 g/m.sup.2, most preferably 1 g/m.sup.2 to 8 g/m.sup.2.

In one embodiment of the present invention, the barrier layer comprisessilicon or silicone containing compound.

3. The Melt Transfer Layer

The melt transfer layer is applied on top of the optionallybarrier-coated support. Any melt transfer layer may be used, forinstance, any of the melt transfer layers disclosed in U.S. Pat. Nos.6,410,200, 6,358,660, 5,501,902, 5,271,990, 5,242,739, 4,021,591,4,555,436, 4,657,557, 4,914,079, 4,927,709, 4,935,300, 5,322,833,5,413,841, 5,679,461, 5,741,387, 5,798,179, 5,603,966, 4,773,953,4,980,224, 5,620,548, 5,139,917, 5,236,801, 5,883,790, 6,245,710,6,083,656, 5,948,586, 6,265,128, 6,033,824, 6,294,307, 6,410,200 and6,358,660, and U.S. application Ser. Nos. 09/366,300, 09/547,760,09/637,082, 09/828,134, 09/980,589, 09/453,881, 09/791,755, 10/089,446,and 10/205,628, and Provisional U.S. Application Ser. Nos. 60/396,632and 60/304,752, all of which are herein incorporated by reference.

Preferably, the melt transfer layer has a slight tack which keeps theimage receiving layer on the optionally barrier-coated support duringhandling. That is, the melt transfer layer preferably has sufficienttack to hold it onto the optionally barrier-coated support. However, thetack must not be so strong as to permanently bond the melt transferlayer to the support. The preferred tack would be similar to that foundwith an adhesive class of polymer coatings known as the removablepressure sensitive adhesives (e.g., 3M “Post-It”). A removable pressuresensitive adhesive is characterized as an adhesive that allows twosurfaces to be separated, reversibly, without damage to either surface.

After printing/copying/drawing, the image receiving layer is peeled awayfrom the support material. During the peeling process, the melt transferlayer comes away with the image receiving layer and will serve as thesource of adhesion during the transfer upon the application of heat.

The melt transfer layer is coated onto the top of the barrier layer. Thethickness ranges from 1 to 5 mils, preferably 1 to 2 mils, mostpreferably about 1.5 mils. The melt transfer layer has a dry coat ofabout 2 to 40 g/m.sup.2 and a thickness of 0.05 to 1.6 mil. A preferreddry coat weight would be 10-30 g/m.sup.2; and, the most preferred coatweight would be 15-25 g/m.sup.2.

In a preferred embodiment, the melt transfer layer is a polyurethanelayer having sufficient thickness that upon melting adheres to thereceptor element. Preferred thickness for the polyurethane layer rangefrom about 1.25 mils to 1.5 mils.

Any polyester, acrylic polymer, polyolefin, polyurethane or copolymerblends may be used that exhibits a melt transition temperature in therange 50° C.-250° C., or when the glass transition temperature (Tg) ofthe polyolefin, polyester, polyurethane, acrylic polymer or copolymerblend is less than about 25 degrees Centigrade. Preferably, the Tg willfall between about 25° C. and 120° C. and display a slight tack whentouched. Non-limiting examples include polyamide (4220; BemisAssociates), polyurethane (5250; Bemis Associates; Estane™ 5700 series,in particular Estane™ 5703 TPU of Noveon, Inc. Cleveland Ohio; or Daotanpolyurethanes by Surface Specialties, Inc. UBC), polyester (UAF-425 orPAF-110; Adhesive Films, Inc.), and polyester (Integral Film 801; DowCo.)

In one embodiment, the melt transfer layer comprises an ethylene vinylacetate/ethylene acrylic acid copolymer blend. In another embodiment,the melt transfer layer comprises a EVA based terpolymer ofethylene-vinyl acetate and maleic anhydride terpolymer. In anotherembodiment, the melt transfer layer comprises polyurethane. Aspects ofthe polyurethane that are important include the softening temperature,softness of the polymer, color of the polymer and elasticity of thepolymer. It is desirable to use a polyurethane that is as soft aspossible, but has high elastic properties. Polyurethane products havinga Shore Hardness between 70A and 90A are preferred. Non-yellowing of themelt transfer layer is important and therefore the polyurethane shouldbe non-yellowing. Aliphatic polyurethanes are more UV stable than otherpolyurethanes such as aromatic polyurethanes and therefore can possessbetter non-yellowing properties.

In one embodiment of the invention, the melt transfer layer comprises anethylene acrylic acid co-polymer dispersion, an elastomeric emulsion, apolyurethane dispersion, and polyethylene glycol. An example of thisembodiment is Melt Transfer Layer Formulation 1.

The acrylic dispersion is present in a sufficient amount so as toprovide adhesion of the melt transfer layer and image to the receptorelement upon application of heat and is preferably present in an amountof from 46 to 90 weight %, more preferably 70 to 90 weight % based onthe total composition of the melt transfer layer.

The elastomeric emulsion provides the elastomeric properties such asmechanical stability, flexibility and stretchability, and is preferablypresent in an amount of from 1 to 45 weight %, more preferably 1 to 20weight % based on the total composition of the melt transfer layer.

The water repellent provides water resistance and repellency, whichenhances the wear resistance and washability of the image on thereceptor, and is preferably present in an amount of from 1 to 7 weight%, more preferably 3 to 6 weight % based on the total composition of themelt transfer layer.

The plasticizer provides plasticity and antistatic properties to thetransferred image, and is preferably present in an amount of from 1 to 8weight %, more preferably 2 to 7 weight % based on the total compositionof the melt transfer layer.

The acrylic dispersion may be an ethylene acrylic acid co-polymerdispersion that is a film-forming binder that provides the “release” or“separation” from the support. The melt transfer layer of the inventionmay utilize the film-forming binders of the image-receptivemelt-transfer film layer of U.S. Pat. No. 5,242,739, which is hereinincorporated by reference.

Thus, the nature of the film-forming binder is not known to be critical.That is, any film-forming binder can be employed so long as it meets thecriteria specified herein. As a practical matter, water-dispersibleethylene-acrylic acid copolymers have been found to be especiallyeffective film forming binders.

The term “melts” and variations thereof are used herein only in aqualitative sense and are not meant to refer to any particular testprocedure. Reference herein to a melting temperature or range is meantonly to indicate an approximate temperature or range at which a polymeror binder melts and flows under the conditions of a melt-transferprocess to result in a substantially smooth film.

Manufacturers' published data regarding the melt behavior of polymers orbinders correlate with the melting requirements described herein. Itshould be noted, however, that either a true melting point or asoftening point may be given, depending on the nature of the material.For example, materials such as polyolefins and waxes, being composedmainly of linear polymeric molecules, generally melt over a relativelynarrow temperature range since they are somewhat crystalline below themelting point.

Melting points, if not provided by the manufacturer, are readilydetermined by known methods such as differential scanning calorimetry.Many polymers, and especially copolymers, are amorphous because ofbranching in the polymer chains or the side-chain constituents. Thesematerials begin to soften and flow more gradually as the temperature isincreased. It is believed that the ring and ball softening point of suchmaterials, as determined by ASTM E-28, is useful in predicting theirbehavior. Moreover, the melting points or softening points described arebetter indicators of performance than the chemical nature of the polymeror binder.

In another embodiment of the invention, the polymer may be applied tooptionally barrier-coated support in powder form, and then, heat isapplied to form a coherent mass of the polymer on the support. Thisprocess is often referred to in the textile industry as powdersintering. Any polyethylene, polyamide or blends thereof may be used inthe process. Vestamelt 350, 432, 730, 732 and 750 (Degussa Corp.) areexamples of a polyolefin polyamide blends with a typical melt transitiontemperature in the range of 105-130° C. Polyethylene powders aretypically low density polyethylene (LDPE) compositions with a melttemperature in the range 50-250° C., preferably 70-190° C. and mostpreferably 80-150° C. LDPE examples include Microthenc F501 (EquistarChemical Co.) with a melt temperature of 104° C., and Icotex 520-5016(Icopolymers Co.) with a melt temperature of 100° C.

Representative melt transfer binders (e.g., acrylic dispersions) forrelease from the support are as follows:

Melt Transfer Binder A

Binder A is Michem® 58035, supplied by Michelman, Inc., Cincinnati,Ohio. This is a 35 percent solids dispersion of Allied Chemical's AC580, which is approximately 10 percent acrylic acid and 90 percentethylene. The polymer reportedly has a softening point of 102° C. and aBrookfield viscosity of 0.65 pas (650 centipoise) at 140° C.

Melt Transfer Binder B

This binder is Michem® Prime 4983R (Michelman, Inc., Cincinnati, Ohio).The binder is a 25 percent solids dispersion of Primacor® 5983 made byDow Chemical Company. The polymer contains 20 percent acrylic acid and80 percent ethylene. The copolymer has a Vicat softening point of 43° C.and a ring and ball softening point of 100° C. The melt index of thecopolymer is 500 g/10 minutes (determined in accordance with ASTMD-1238).

Melt Transfer Binder C

Binder C is Michem® 4990 (Michelman, Inc., Cincinnati, Ohio). Thematerial is 35 percent solids dispersion of Primacor® 5990 made by DowChemical Company. Primacor® 5990 is a copolymer of 20 percent acrylicacid and 80 percent ethylene. It is similar to Primacor® 5983 (seeBinder B), except that the ring and ball softening point is 93° C. Thecopolymer has a melt index of 1,300 g/10 minutes and Vicat softeningpoint of 390 C.

Melt Transfer Binder D

This binder is Michem® 37140, a 40 percent solids dispersion of aHoechst-Celanese high density polyethylene. The polymer is reported tohave a melting point of 100° C.

Melt Transfer Binder E

This binder is Michcm® 32535 which is an emulsion of Allied ChemicalCompany's AC-325, a high density polyethylene. The melting point of thepolymer is about 138° C. Michem® 32535 is supplied by Michelman, Inc.,Cincinnati, Ohio.

Melt Transfer Binder F

Binder F is Michem® 48040, an emulsion of an Eastman Chemical Companymicrocrystalline wax having a melting point of 88° C. The supplier isMichelman, Inc., Cincinnati, Ohio.

Melt Transfer Binder G

Binder G is Michem® 73635M, an emulsion of an oxidized ethylene-basedpolymer. The melting point of the polymer is about 96° C. The hardnessis about 4-6 Shore-D. The material is supplied by Michelman Inc.,Cincinnati, Ohio.

The second component of Melt Transfer Layer Formulation 1 is anelastomeric emulsion, preferably a latex, and is compatible with theother components, and formulated to provide durability, mechanicalstability, and a degree of softness and conformability to the layers.

Films of this material must have moisture resistance, low tack,durability, flexibility and softness, but with relative toughness andtensile strength. Further, the material should preferably have inherentheat and light stability. The latex can be heat sensitized, and theelastomer can be self-crosslinking or used with compatible cross-linkingagents, or both. The latex should be sprayable, or roll stable forcontinuous runnability on nip rollers.

Elastomeric latexes of the preferred type are produced from thematerials and processes set forth in U.S. Pat. Nos. 4,956,434 and5,143,971, which are herein incorporated by reference. This curablelatex is derived from a major amount of acrylate monomers such as C₄ toC₈ alkyl acrylate, preferably n-butyl acrylate, up to about 20 parts perhundred of total monomers of a monolefinically unsaturated dicarboxylicacid, most preferably itaconic acid, a small amount of crosslinkingagent, preferably N-methyl acrylamide, and optionally anothermonolefinic monomer.

Using a modified semibatch process in which preferably the itaconic acidis fully charged initially to the reactor with the remaining monomersadded over time, a latex of unique polymer architecture or morphology iscreated, leading to the unique rubbery properties of the cured filmsproduced therefrom.

The third ingredient of Melt Transfer Layer Formulation 1 is a waterresistant and adhesion aid such as a polyurethane dispersion.Preferably, the polyurethane will be a self-crosslinking formulationincorporating crosslinking agents such as melamine. This ingredient isalso a softener for the acrylic dispersion and plasticizer aid.

Such polyurethane product may be produced by polymerizing one or moreacrylate and other ethylenic monomers in the presence of anoligourethane to prepare oligourethane acrylate copolymers. Theoligourethane is preferably prepared from diols and diisocyanates, thealiphatic or alicyclic based diisocyanates being preferred, with lesseramounts, if any, of aromatic diisocyanates, to avoid components whichcontribute to yellowing. Polymerizable monomers, in addition to theusual acrylate and methacrylate esters of aliphatic monoalcohols andstyrene, further include monomers with carboxyl groups, such as acrylicacid or methacrylic acid, and those with other hydrophylic groups suchas the hydroxyalkyl acrylates (hydroxyethyl methacrylate beingexemplary). The hydrophylic groups in these monomers render thecopolymer product dispersible in water with the aid of a neutralizingagent for the carboxyl groups, such as dimethylethanolamine, used inamount to at least partially neutralize the carboxyl groups afterdispersion in water and vacuum distillation to remove any solvents usedto prepare the urethane acrylic hybrid. Further formulations may includethe addition of crosslinking components such as amino resins, strainedamines or blocked polyisocyanates. Although pigments and fillers couldbe added to any of the coating layers, such use to uniformly tint orcolor the web could be used for special effect, but would not be usedwhere an image is desired in the absence of background coloration.Urethane acrylic hybrid polymers are further described in U.S. Pat. No.5,708,072, and their description in this application is incorporated byreference.

Self crosslinking acrylic polyurethane hybrid compositions can also beprepared by the processes and materials of U.S. Pat. No. 5,691,425,herein incorporated by reference. These are prepared by producingpolyurethane macromonomers containing acid groups and lateral vinylgroups, optionally terminal vinyl groups, and hydroxyl, urethane,thiourethane and/or urea groups. Polymerization of these macromonomersproduces acrylic polyurethane hybrids which can be dispersed in waterand combined with crosslinking agents for solvent-free coatingcompositions.

Autocrosslinkable polyurethane-vinyl polymers are discussed in detail inU.S. Pat. No. 5,623,016 and U.S. Pat. No. 5,571,861, and theirdisclosure of these materials is incorporated by reference. The productsusually are polyurethane-acrylic hybrids, but with self-crosslinkingfunctions. These may be carboxylic acid containing, neutralized with,e.g. tertiary amines such as ethanolamine, and form useful adhesions andcoatings from aqueous dispersion.

The elastomeric emulsion and polyurethane dispersion are, generally,thermoplastic elastomers. Thermoplastic elastomeric polymers are polymerblends and alloys which have both the properties of thermoplasticpolymers, such as having melt flow and flow characteristics, andelastomers, which are typically polymers which cannot melt and flow dueto covalent chemical crosslinking (vulcanization) or regions (blocks) ofhighly ordered polymeric units. Thermoplastic elastomers are generallysynthesized using two or more monomers that are incompatible; forexample, styrene and butadiene. By building long runs of polybutadienewith intermittent polystyrene runs, microdomains are established whichimparts the elastomeric quality to the polymer system. However, sincethe microdomains are established through physical crosslinkingmechanisms, they can be broken by application of added energy, such asheat from a hand iron, and caused to melt and flow; and therefore, areelastomers with thermoplastic quality.

Thermoplastic elastomers have been incorporated into the presentinvention in order to provide the image system with elastomeric quality.Two thermoplastic elastomer systems have been introduced; that is, apolyacrylate terpolymer elastomer (for example, Hystretch V-29) and analiphatic urethane acryl hybrid (for example, Daotan VTW 1265).Thermoplastic elastomers can be chosen from a group that includes, forexample, ether-ester, olefinic, polyether, polyester and styrenicthermoplastic polymer systems. Specific examples include, by way ofillustration, thermoplastic elastomers such as polybutadiene,polybutadiene derivatives, polyurethane, polyurethane derivatives,styrene-butadiene, styrene-butadiene-styrene, acrylonitrile-butadiene,acrylonitrile-butadiene-styrene, acrylonitrile-ethylene-styrene,polyacrylates, polychloroprene, ethylene-vinyl acetate and poly (vinylchloride). Generally, thermoplastic elastomers can be selected from agroup having a glass transition temperature (Tg) ranging from about −50°C. to about 25° C.

Although polyurethane is one component of one of the embodiments of thepresent melt transfer layer, the melt transfer layer may comprisespolyurethane as the main or single component. For instance, reference ismade to Melt Transfer Layer Formulations 3 and 4. The melt transferlayer as a polyurethane layer preferably has sufficient thickness thatupon melting adheres to the receptor element. Preferred thickness forthe polyurethane layer range from about 1.25 mils to 1.5 mils.

The fourth component of Melt Transfer Layer Formulation 1 is aplasticizer such as a polyethylene glycol dispersion which providesmechanical stability, water repellency, and allows for a uniform,crack-free film. Accordingly, a reason to add the polyethylene glycoldispersion is an aid in the coating process. Further, the polyethyleneglycol dispersion acts as a softening agent. A preferred fourthcomponent is Carbowax Polyethylene Glycol 400, available from UnionCarbide.

An optional fifth ingredient of Melt Transfer Layer Formulation 1 is asurfactant and wetting agent such as polyethylene glycol mono((tetramethylbutyl) phenol) ether. Alternatively, the representativebinders, described above that are suitable for Melt Transfer LayerFormulation 1, may be used in lieu of the above-described ethyleneacrylic acid copolymer dispersion.

In a one embodiment, the melt transfer layer is composed of acrosslinking polymer, for example, polyurethane or polyethylene. Whenheat is applied to the melt transfer layer, it bonds to the receptorelement. The bond created is durable to washing, dry-cleaning, and isdurable under mechanical stress.

5. Optional Opaque Layer(s)

The present material may optionally contain one or more opaque layers,for instance the opaque layers described in pending U.S. patentapplication Ser. Nos. 10/089,446 and 10/483,387. In the presentinvention, the optional opaque layer(s) is placed between the melttransfer layer and the image receiving layer.

The optional opaque layer(s) adds a rigid or stiff quality to thetransfer sheet for ease of handling, as well as having opacity,especially white, to enhance visibility of the image when placedthereon. That is, the opaque layer(s) aid in ink visibility on variouscolored receptors.

Note that, if desired, when one or more opaque layers is used betweenthe melt transfer layer and the image receiving layer, the use of thesupport and barrier layer become optional. The support and barrier layermay be used to facilitate the preparation of an image transfer materialhaving a melt transfer layer, one or more opaque layers and an imagereceiving layer, however, the product itself need only contain one ormore opaque layers with a melt transfer layer on one side and an imagereceiving layer on the other. The one or more opaque layers provide thenecessary rigidity that would normally be supplied by the support.

The thickness of the one or more opaque layers, when no support layer ispresent, should be sufficient to provide necessary thickness andrigidity for the intended use or mode of imaging of the transfer paper.Depending upon the intended use, the thickness and rigidity will vary.For example, if intended to be imaged with a printer, e.g., an ink jetprinter, the combination of the melt transfer layer, one or more opaquelayer and image receiving layer preferably have sufficient rigidity toas to pass through the printer without substantial damage. Exemplarythickness of an opaque layer in such an instance range from about 0.5mils to about 2.5 mils.

5.1 Opaque Layer A

When one or more opaque layers are employed, the opaque layer providesadditional background contrast for the applied image to render itvisible against, for instance a dark or a light receptor. The opaquelayer(s) improves the appearance and readability of an image, such as,for instance, a bar code or a color image.

When permanently adhering the image material to a textile, the opaquelayer(s) layers preferably will be thermoplastic and optionallythermosetting as they are applied to a porous substrate such as afabric. When a thermosettable formulation is employed for the opaquelayers, the image fused into the fabric will have the maximum resistanceto washing or dry cleaning.

The first optional opaque layer (Opaque layer A) adds a rigid or stiffquality to the entire heat-setting label sheet for ease of handling, aswell as having a white (or colored) opacity. Any pigmented resin may beused to achieve the desired outcome.

A preferred embodiment of opaque layer A, Opaque Layer formulation 1comprises styrene-butadiene latex, thermoplastic elastomer, an elastomerand an optional pigment.

All the above chemicals form a homogeneous dispersion aided by a stirbar at a low to medium stir rate. All mixing can be done at roomtemperature. After coating, the preferred thickness of Opaque Layer A isabout 1.5 mils (wet).

In the above-described preferred embodiment, a pigment such as a whitepigment may be used to exhibit opacity capabilities. Also in thepreferred embodiment, the latex is the primary chemical imparting therigid characteristics upon drying. The thermoplastic elastomer andacrylonic copolymer impart stretchability and flexibility in the finaltransferred product.

5.2 Opaque Layer B

The optional Opaque Layer B preferably contains a pigment (such as awhite pigment) and provides opacity. A preferred embodiment of theoptional opaque layer B. Opaque Layer Formulation 1, comprises a vinylacetate-ethylene copolymer, thermoplastic elastomer, an elastomer and anoptional pigment such as TiO₂.

The thermoplastic elastomer acrylonitrile copolymer impartstretchability and flexibility in the final transferred product.Practically any TiO₂ powder addition, present at about 25% of the totalformula, will provide the desired opacity. Other powdered pigments mayneed to be added at varying percentages to achieve the desired opacityand color intensity.

All liquid chemicals are homogenized in the presence of a stir bar and alow speed. Upon homogenization, the pigment powder is added slowly inthe presence of a high stir speed provide by a stir flea. All mixing ofthe above ingredients should be performed at room temperature.Preferably, optional Opaque Layer B is coated on the heat setting labelsheet at a weight of about 1.0 to 1.5 mils (wet).

6. The Image Receiving Layer

An image receiving layer is applied over the melt transfer layer. Theimage receiving layer formulations of the present invention should beable to retain an image such as an image dye. The image receiving layerretains dyes, such as ink from ink jet printers, or dyes from awaterbased marker. If an ink jet ink is utilized, the image preferablyhas comparable resolution to standard ink jet paper. In one embodiment,the image receiving layer may become heat activated (e.g. melt and flow)to trap or encapsulate the dye image or ink and optionally impartwaterfast characteristics.

The image receiving layer may be applied to the melt transfer layereither by a conventional saturating process such as a “dip and squeeze”process or with a coating process such as a reverse roll, meyer rod,gravure, slot die and the like.

The basis weight of the image receiving layer may vary from about 2 toabout 30 g/m.sup.2. Desirably, the basis weight will be from about 3 toabout 20 g/m.sup.2.

The image receiving layer is capable of heat sealing the image uponapplication of heat up to 220° C. “Heat sealing” as defined hereinrefers to a process whereby the polymer composition melts and flows soas to effectively encapsulate the image forming colorants therein. Heatsealing imparts waterfastness and washability. A heat sealed image wouldhave newly imparted image permanence properties such as waterfastnessand rub resistance. In one embodiment, the image receiving formulationincludes a self-crosslinking polymer as a binder, for instance, Binder Fbelow. In this embodiment, although not all components of the imagereceiving layer will technically melt, for instance, the self-crosslinking EVA polymer will not melt, the layer will still heat seal theimage.

The image receiving layer comprises binders, such as polyvinyl alcohol(PVOH), polyesters, polyurethanes, or co-polymer blends, variouscolorant retention aids, various optional crosslinking agents, anoptional antioxidant, or an optional softening agent.

The binder imparts colorant retention and mechanical stability. A listof applicable binders include, but are not limited to, those listed inU.S. Pat. No. 5,798,179, in addition to polyolefins, polyesters,ethylene-vinyl acetate copolymers, ethylene-methacrylate acidcopolymers, and ethylene-acrylic acid copolymers. The binder may also beselected from the list, mentioned herein, for use in the melt transferlayer.

Preferably, the binder is one of a self-crosslinkable acrylic copolymer,for instance, Rhoplex™ NW-1402, Rhoplex™ HA-16 or RhopleX™ HA-12 fromthe Rohm and Haas Corporation, or a hydrolyzed polyvinyl alcohol, forinstance, Celvol™ 540 or Celvol™ 125, from the Celanese Corporation, ora self-crosslinking ethylene-vinyl acetate copolymer, for instance,Dur-o-Set™ Elite Plus 25-299A, from Vinamul Polymers Corp.

The self-crosslinkable polymer binder is preferably present in anamount, based on the dry solids content of the layer, of 15-40%, andmost preferably 25-35% by weight. In a preferred embodiment, theself-crosslinkable polymer binder is a thermosetting polymer such as aself-crosslinking ethylene vinyl acetate copolymer (for instance,Dur-o-Set™ Elite Plus 25-299A, from Vinamul Polymers Corp.).

Representative image receiving layer binders suitable to impart colorretention and mechanical stability include:

Image Receiving Layer Binder A

Image Receiving Layer Binder A is Rhoplex NW-1402, a self-crosslinkableacrylic copolymer from the Rohm and Haas Corporation. This material is a45% solids formulation with a specific gravity of 1.0 to 1.2.

Image Receiving Layer Binder B

Image Receiving Layer Binder B is Rhoplex HA-16, a self-crosslinkableacrylic copolymer from the Rohm and Haas Corporation. This material is a46% solids formulation with a maximum viscosity of 900 CPS.

Image Receiving Layer Binder C

Image Receiving Layer Binder C is Rhoplex HA-12, a self-crosslinkableacrylic copolymer from the Rohm and Haas Corporation. This material is a46% solids formulation with a maximum viscosity of 750 CPS.

Image Receiving Layer Binder D

Image Receiving Layer Binder D is Celvol 540, a partially hydrolyzedpolyvinyl alcohol from the Celanese Corporation.

Image Receiving Layer Binder E

Image Receiving Layer Binder E is Celvol 125, a hydrolyzed polyvinylalcohol from the Celanese Corporation.

Image Receiving Layer Binder F

Image Receiving Layer Binder F is Dur-o-set 25-299A, a self-crosslinkingEVA copolymer from Vinamul Polymers Corp. This materials is prepared asa 50% solids emulsion with a bulk density of 8.9 lb/gal.

Thermoplastic binders, other than the self-crosslinkable polymersdiscussed above, may also be incorporated. For instance, any of thethermoplastic binders listed above for the melt transfer layer may beincorporated. For instance, thermoplastic binders, such as those listedabove may be incorporated in amounts of 5-40%, preferably 10-30% byweight based on the dry solids content.

Additionally, a polyamide copolymer, for instance, a nylon copolymer maybe added to the image receiving layer. For instance nylon 6-12 (Orgasol™3501 EXDNAT 1, from Atofina), nylon 12 (Orgasol 2002 EXDNAT 1, fromAtofina), and nylon 6 (Orgasol 1002 DNAT1, from Atofina). Theformulation may also include a polyvinylpyrrolidone (PVP) polymer andcopolymer blends for instance, Luvicross (BASF), Luvicross M (BASF),Luvicross VI (a PVP-vinyl imidazole copolymer blend (BASF)), and Luvitec(BASF). The polyamide copolymers may be incorporated in amounts of5-40%, preferably 10-30% by weight based upon the dry solids of theformulation.

Silica may also be added to the image receiving layer. Silica is silicondioxide, and can generally be any preparation that has a mean diameternot larger than 100 microns. Examples include the Syloid brand of silica(such as Syloid W-500, from Grace Davidson Co.), Sylojet brand of silica(such as the Sylojet P400, Grace Davidson Co.), INEOS silica (such asthe Gasil HP270 or Gasil IJ45). Silica may be added in amounts rangingfrom 5-60%, preferably 10-40%, most preferably 15-35% by weight based onthe dry solids content.

An antioxidant may be added to keep the binder from discoloring(yellowing) during the heat process. Suitable antioxidants include, butare not limited to, BHA; Bis(2,4-di-t-butylphenyl)pentaerythritoldiphosphite; 4,4′-Butylidenebis(6-t-butyl-m-cresol), C20-40 alcohols;p-Crescol/dicyclopentadiene butylated reaction product, Di(butyl, methylpyrophosphato)ethylene titanate di(dioctyl, hydrogen phosphite);Dicyclo(dioctyl)pyrophosphato titanate; Di(dioctylphosphato) ethylenetitanate; Di(dioctylpyrophosphato)ethylene titanate; Disobutylnonylphenol; Dimethylaminomethyl phenol, Ethylhydroxymethyloleyl oxazolineIsopropyl 4aminobenzenesulfonyl di(dodecylbenzenesulfonyl)titanate;Isopropyldimethacrylisoslearoyl titanate; Isopropyl(dioctylphosphato)titanate; isopropyltridioctylpyrophosphato) titanate;Isopropyl tri(N ethylamino-ethylamino)titanate, Lead phthalate, basic2,2-Methylenebis (6-t-butyl-4-methylphenol), Octadecyl3,5-di-t-butyl-4-hydroxyhydrocinnamate Phosphorus; Phosphorustrichloride, reaction prods. with 1,1′-biphenyl and 2,4-bis(1,1-dimethylethyl)phenol Tetra (2, diallyoxymethyl-1 butoxy titaniumdi(di-tridecyl)phosphite; Tetraisopropyl di(dioctylphosphito)titanate;Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane;Tetraoctyloxytitanium; di(ditridecylphosphite);4,4′-Thiobis-6-(t-butyl-m-cresol); Titanium di(butyl, octylpyrophosphate) di(dioclyl, hydrogen phosphite)oxyacetate; Titaniumdi(cumylphenylate)oxyacetate; Titaniumdi(dioctylpyrophosphate),oxyacelate; Titanium dimethyacrylate oxyacetate;2,2,4-Trimethyl-1,2-dihydro-quinoline polymer; Tris(nonylphenyl)phosphite. Preferably, the antioxidant used is octadecyl3,5-Ditert-butyl-4-hydroxyhydrocinnamate.

An optional crosslinking agent can be added to each formula to crosslinkthe binder to improve waterfastness. Crosslinkers suited for thisapplication including, but not limited to, aziridine (ie., IonacPFAZ-322), aziridine derivatives, multifunctional aziridines (XAMA-7(Sybron)) Sancure 777 (Noveon), and melamine (ie., Cymul 323 EvCo,Inc.), and organometallics like an organic titanate such as Tyzor LA(DuPont).

The self-crosslinkable polymer binder-containing image receivingformulation may further include dye retention aids, such as a cationicpolymer. Other dye retention aids include the silica listed above, thepolyamide copolymer and PVA. The cationic polymer may be incorporated inamounts of 1-10% by weight, preferably 1-4% by weight based upon the drysolids content of the layer. Other dye retention aids may include anysalt with dissociative properties. Exemplary, but non-limitive examplesinclude salts with Group II elements such as Mg, CA, Sr or Ba, or otherelements such as Al, Zn, and Cu. Preferably CaCl₂ may be utilized as adye retention aid. The salt with dissociative properties may be presentin amounts of 0.25-4%, preferably 1-2% by weight based upon the dryweight of the formulation. The cationic polymer may be, for example, anamide-epichlorohydrin polymer, polyacrylamides with cationic functionalgroups, polyethyleneimines, polydiallylamines, and the like.

Representative cationic polymers used as a dye retention aid include:

Cationic Polymer A

Cationic Polymer A is APC-M1, a polydiallylmethylamine hydrochlorideresin from Advanced Polymers, Inc. APC-M1 is a 60% solids dispersion inwater with a molecular weight of 20,000.

Cationic Polymer B

Cationic Polymer B is APC-J81, a dimethyldiallylammoniumchloride/acrylamide copolymer from Advanced Polymers, Inc. APC-J81 is a25% solids dispersion in water with a molecular weight of 200,000.

Cationic Polymer C

Cationic Polymer C is APC-A1, a dimethyldiallylammonium chloride/sulfurdioxide copolymer from Advanced Polymers, Inc. APC-A1 is a 24% solidsdispersion in water with a molecular weight of 5,000.

Cationic Polymer D

Cationic Polymer D is CP 7091 RV, a poly(diallyldimethylammoniumchloride-co-diacetone acrylamide) from ECC International.

When a cationic polymer is present, a compatible binder should beselected, such as a nonionic or cationic dispersion or solution. As iswell known in the paper coating art, many commercially available bindershave anionically charged particles or polymer molecules. These materialsare generally not compatible with the cationic polymer which may be usedin the image receiving layer.

The image receiving layer may contain the addition of filler agents withthe purpose of opacifying and modulating the surface characteristics ofthe present invention. The surface roughness and coefficient of frictionmay need to be modulated depending on such factors as desired surfacegloss and the imaging device's specific paper feeding requirements. Thefiller can be selected from a group of polymers such as, for example,polyacrylates, polyacrylics, polyethylene, polyethylene acryliccopolymers and polyethylene acrylate copolymers, vinyl acetatecopolymers and polyvinyl polymer blends that have various particledimensions and shapes. Typical particle sizes may range from 0.1 to 500microns. Preferably, the particle sizes range from 5 to 100 microns.More preferably, the particle sizes range from 5 to 30 microns. Thefiller may also be selected from a group of polymers such as, forexample, cellulose, hydroxycellulose, starch and dextran. Silicas andmica may also be selected as a filler. The filler is homogeneouslydispersed in the image receiving layer in concentrations ranging from0.1 to 50%. Preferably, the filler concentration range is 1 to 10percent. The filler may also be an inorganic pigment such as titaniumdioxide.

The image receiving layer may also contain viscosity modifiers andanti-foaming agents. An example of a viscosity modifier is a Laponiteproduct by Southern Clay Products, Inc., Gonzales, Tex.; or Alcogum®L-520 (Alco Chemical).

7. Optional Antistatic Layer

An antistatic layer may be coated on the back of the support oppositethe melt transfer layer. Any suitable antistatic layer known in the artmay be used as the antistatic layer of the present invention. Inaccordance with one embodiment of the invention, the support is usablein a laser copier or laser printer. A preferred support for thisembodiment is equal to or less than approximately 4.0 mils thick. Theantistatic layer according to the present invention may have a solutionviscosity of from 0.1 to 20 cP, preferably 1-5 cP, most preferably about2 cP, as measured on a Brookfield DV-I+ viscometer, LV1 spindle at 60rpm at a temperature of 25° C. Additionally, the antistatic layer may bewet coated in an amount of from 1 g/m.sup.2 to 50 g/m.sup.2, preferablyfrom 10-30 g/m.sup.2, most preferably about 18 g/m.sup.2. The surfacetension of the antistatic layer may be from 30-110 dynes/cm, preferablyfrom 50-90 dynes/cm, most preferably about 70 dynes/cm as measured atroom temperature.

Since the support is useable in a laser copier or laser printer,antistatic agents may be present. The antistatic agents may be presentin the form of a coating on the back surface of the support as anadditional layer. The back surface of the support is the surface that isnot previously coated with the melt transfer layer.

When the antistatic agent is applied as a coating onto the back surfaceof the support, the coating will help eliminate copier or printerjamming by preventing the electrostatic adhesion of the paper base tothe copier drum of laser and electrostatic copiers and printers.Antistatic agents, or “antistats” are generally, but not necessarily,conductive polymers that promote the flow of charge away from the paper.Antistats can also be “humectants” that modulate the level of moisturein a paper coating that affects the build up of charge. Antistats arecommonly charged tallow ammonium compounds and complexes, but also canbe complexed organometallics. Antistats may also be charged polymersthat have a similar charge polarity as the copier/printer drum; wherebythe like charge repulsion helps prevent jamming.

Antistatic agents include, by way of illustration, derivatives ofpropylene glycol, ethylene oxide-propylene oxide block copolymers,organometallic complexes such as titanium dimethylacrylate oxyacetate,polyoxyethylene oxide-polyoxypropylene oxide copolymers and derivativesof cholic acid.

More specifically, commonly used antistats include those listed in theHandbook of Paint and Coating Raw Materials, such as t-Butylaminoethylmethacrylate; Capryl hydroxyethyl imidazoline; Cetethyl morpholiniumethosulfate; Cocoyl hydroxyethyl imidazoline Di(butyl, methylpyrophosphato) ethylenetitanate di(dioctyl, hydrogen phosphite);Dicyclo(dioctyl)pyrophosphato; titanate; Di(dioctylphosphato)ethylenetitanate; Dimethyl diallyl ammonium chloride; Distearyldimoniumchloride; N,N′-Ethylene bis-ricinoleamide; Glyceryl mono/dioleate;Glyceryl oleate; Glyceryl stearate; Heptadecenyl hydroxyethylimidazoline; Hexyl phosphate; N(.beta.-Hydroxyethyl)ricinoleamide;N-(2-Hydroxypropyl)benzenesulfonamide; Isopropyl4-aminobenzenesulfonyldi(dodecylbenzenesulfonyl)titanate; Isopropyl dimethacryl isostearoyltitanate; isopropyltri(dioctylphosphato)titanate; Isopropyltri(dioctylpyrophosphato)titanate; Isopropyl tri(Nethylaminoethylamino)titanate; (3-Lauramidopropyl)trimethyl ammoniummethyl sulfate; Nonyl nonoxynol-15; Oleyl hydroxyethylimidazoline;Palmitic/stearic acid mono/diglycerides; PCA; PEG-36 castor oil; PEG-10cocamine; PEG-2 laurate; PEG-2; tallowamine; PEG-5 tallowamine; PEG-15tallowamine; PEG-20 tallowamine; Poloxamer 101; Poloxamer 108; Poloxamer123; Poloxamer 124; Poloxamer 181; Poloxamer 182; Poloxamer 184;Poloxamer 185; Poloxamer 188; Poloxamer 217; Poloxamer 231; Poloxamer234; Poloxamer 235; Poloxamer 237; Poloxamer 282; Poloxamer 288;Poloxamer 331; Polaxamer 333; Poloxamer 334; Poloxamer 335; Poloxamer338; Poloxamer 401; Poloxamer 402; Poloxamer 403; Poloxamer 407;Poloxamine 304; Poloxamine 701; Poloxamine 704; Polaxamine 901;Poloxamine 904; Poloxamine 908; Poloxamine 1107; Poloxamine 1307;Polyamide/epichlorohydrin polymer; Polyglyceryl-lo tetraoleate;Propylene glycol laurate; Propylene glycol myristate; PVM/MA copolymer;polyether; Quaternium-18; Slearamidopropyl dimethyl-.beta.-hydroxyethylammonium dihydrogen phosphate; Stearamidopropyl dimethyl-2-hydroxyethylammonium nitrate; Sulfated peanut oil; Tetra (2, diallyoxymethyl-1butoxy titanium di(di-tridecyl)phosphite; Tetrahydroxypropylethylenediamine; Tetraisopropyl di(dioctylphosphito)titanate;Tetraoctyloxytitanium di(ditridecylphosphite); Titanium di(butyl, octylpyrophosphate) di(dioctyl, hydrogen phosphite)oxyacetate; Titaniumdi(cumylphenylate)oxyacetate; Titaniumdi(dioctylpyrophosphate)oxyacetate; Titanium dimethacrylate oxyacetate.

Preferably, Marklear AFL-23 or Markstat AL-14, polyethers available fromWhitco Industries, are used as an antistatic agents.

The antistatic coating may be applied on the back surface of the supportby, for example, spreading a solution comprising an antistatic agent(i.e., with a metering rod) onto the back surface of the support andthen drying the support.

An example of one support of the present invention is Georgia Pacificbrand Microprint Laser Paper. However, any non-woven cellulosic or filmsupport may be used as the support in the present invention.

B. Application of Layers

The various layers of the transfer material are formed by known coatingtechniques, such as by curtain coating, Meyer rod, roll, blade, airknife, cascade and gravure coating procedures. In addition, it is alsopossible to apply the melt transfer layer by extrusion coating orlamination.

In referring to FIG. 1, there is generally illustrated a cross-sectionalview of one embodiment of the transfer sheet of the present invention.The support 21 comprises a top and bottom surface. On the top surface ofthe support is the barrier layer 22. On top of the barrier layer is themelt transfer layer 23. On top of the melt transfer layer is the imagereceiving layer 24. The image 25 is placed over the image receivinglayer 24 on the side opposite the support material. An optionalanti-static 26 layer may be coated on the bottom surface of the support21.

The melt transfer layer may either be extrusion coated or laminated ontothe barrier layer. These are performed by methods conventional in theart.

C. Receptor Element

The receptor or receiving element receives the transferred image. Asuitable receptor includes but is not limited to textiles includingcotton fabric, and cotton blend fabric. The receptor element may alsoinclude glass, metal, wool, plastic, ceramic or any other suitablereceptor. Preferably the receptor element is a tee shirt or the like.

The image, as defined in the present application may be applied in anydesired manner. For example, the image may be formed by a color ormonochrome laser printer, laser copier, bubblejet printer, inkjetprinter, and the like. The image may also be applied using commercialprinting methods such as sheet-fed offset, screen and gravure printingmethods or with crayons or markers.

To transfer the image, several alternatives exist. For instance, thetransfer material may be first imaged. Then, the imaged image receivinglayer and melt transfer layer are peeled away from the support materialand placed preferably image side up, melt transfer layer down, against areceptor element.

Alternatively, the image receiving layer and melt transfer layer may befirst peeled away from the support layer. Then, the peeled imagereceiving layer and melt transfer layer may be imaged, with the imagebeing applied to the image receiving layer side of the peeled material.Then, the imaged image receiving layer and melt transfer layer areplaced preferably image side up, melt transfer layer down, against areceptor element.

Alternatively, imaging step can wait until after the peeled imagereceiving layer and melt transfer layer are placed upon the receptor. Inthis alternative, the image receiving layer and melt transfer layer arepreferably placed melt transfer layer down.

Alternatively, after an imaged image receiving layer and melt transferlayer are placed upon the receptor element, additional imaging mayoccur.

Alternatively, when one or more opaque layers is present between themelt transfer layer and the image receiving layer, the combination ofthe melt transfer layer, one or more opaque layer, and image receivinglayer may first be optionally imaged and peeled from the support. Or thecombination of the melt transfer layer, one or more opaque layer, andimage receiving layer may be separately, without a support and thenoptionally imaged. Or, after an optionally imaged image receiving layer,one or more opaque layer and melt transfer layer are placed upon thereceptor element, additional imaging may occur.

After the image receiving layer and melt transfer layer (or possibly theimage receiving layer, one or more opaque layer and melt transfer layer)are placed on the receptor element, whether they are imaged or not, thenext step is that a heat source, for instance a hand iron, a heat pressor an oven is used to apply heat to the top imaged surface which in turnreleases the image. If a hand iron or heat press is used that is notmade of a tack-free material (such that the imaged material layer willstick thereto), a non-stick sheet should be placed between the heatsource and the imaged material. However, even if the heat source, be ita hand iron or heat press, is made of a tack-free material, a non-sticksheet may still be placed between the heat source and the imagedmaterial.

Alternatively, heat may be applied to the back surface of the receptorelement. In this alternative there is no need for a tack-free sheetregardless of the heat source used.

The temperature transfer range of the hand iron is generally in therange of 110 to 220° C. with about 190° C. being the preferredtemperature. The heat press operates at a temperature transfer range of100 to 220° C. with about 190° C. being the preferred temperature.Lastly, if a conventional oven is used, the temperature should be setwithin the range of 110 to 220° C. with about 190° C. being thepreferred temperature

In the hand iron or heat press transfer, the heat source is preferablyplaced over the imaged side of peeled image receiving layer and melttransfer layer. However, as indicated above, the hand iron or heat pressmay be applied to the side of the receptor element opposite the peeledlayer. With a hand iron, the iron is preferably moved in a circularmotion. Pressure (i.e., typical pressure applied during ironing) shouldbe applied as the heating device is moved over the support (see FIG. 2).For a 8.5.times.11 (US Letter) inch web, heat is applied for about twominutes to five minutes (with about three minutes being preferred) usinga hand iron and 10 seconds to 50 seconds using a heat press (with abouttwenty seconds being preferred) of heat and pressure, the transfershould be complete. The heating time requirement may be proportionallyshorter or longer depending on the web size. The optional non-sticksheet is removed either prior to cooling or after cooling. The non-sticksheet is not required if the heating device is made of a non-stickmaterial.

Referring to FIG. 2, the method of applying an image to a receptorelement will be described. More specifically, FIG. 2 illustrates how thestep of heat transfer from the transfer sheet 50 to a tee shirt orfabric 62 may be performed. A tee shirt 62 is laid flat, as illustrated,on an appropriate support surface, and the optionally imaged surface ofthe peeled image receiving layer and melt transfer layer is preferablypositioned up and away from the tee shirt. A non-stick layer is thenplaced on top of the peeled imaged material. An iron 64 set at itshighest heat setting is run and pressed across the non-stick sheet. Theimage is transferred to the tee shirt and the non-stick sheet is removedand discarded or saved for reuse. The non-stick sheet is not required ifthe heating device is made of a non-stick material.

The non-stick sheet is any non-stick or tack-free sheet in the artincluding but not limited to a silicone sheet, a sheet coated with abarrier layer according to the present invention, or a substrate orsupport sheet.

In a preferred embodiment, the method of ironing as described in U.S.Pat. No. 6,539,652, which is herein incorporated by reference, can beused.

The following examples are provided for a further understanding of theinvention, however, the invention is not to be construed as limitedthereto.

EXAMPLES Example 1

In one embodiment of the invention, the melt transfer layer is anethylene acrylic acid co-polymer. An example of this embodiment is MeltTransfer Layer Formulation 1:

Melt Transfer Layer Formulation 1 Components Parts by weight EthyleneAcrylic Acid 86 parts Co-polymer Dispersion (Michem Prime 4983R,Michelman) Elastomeric emulsion 5 parts (Hystretch V-29, B F Goodrich)Polyurethane Dispersion (Daotan 4 parts VTW 1265, Vianova Resins)Polyethylene Glycol (Carbowax 4 parts Polyethylene Glycol 400, UnionCarbide) Polyethylene Glycol Mono 1 part ((Tetramethylbutyl) Phenol)Ether (Triton X-100, Union Carbide)

Melt Transfer Layer Formulation 1, as an embodiment of the inventionsuitable for at least laser copiers and laser printers, is wax free.Melt Transfer Layer Formulation 1 may be prepared as follows: five partsof the elastomer dispersion are combined with eighty-six parts of anethylene acrylic acid co-polymers dispersion by gentle stirring to avoidcavitation. Four parts of a polyurethane dispersion are then added tothe mixture. Immediately following the addition of a polyurethanedispersion, four parts of a polyethylene glycol and one part of annonionic surfactant (e.g., Triton X-100) are added. The entire mixtureis allowed to stir for approximately fifteen minutes at a moderate stirrate (up to but not exceeding a rate where cavitation occurs).

Example 2

This example relates to another melt transfer layer formulation, MeltTransfer Layer Formulation 2.

Melt Transfer Layer Formulation 2 Components Parts Etbylene Acrylic Acid74 parts (weight) Co-polymers dispersion (Michem Prime 4938R, Michelman)Wax Dispersion (Michelman 73635M, 25 parts (weight) Michelman)

Melt Transfer Layer Formulation 2 may be prepared in the followingmanner: the ethylene acrylic acid co-polymer dispersion and the waxdispersion are stirred (for example in a beaker with a stirring bar).

Example 3

This example relates to another melt transfer layer formulation, MeltTransfer Layer Formulation 3.

Melt Transfer Layer Formulation 3 Components Parts Heat -activatedPolyurethane Dispersion 100 Parts (Neorez R-551 (Avecia Co.)

Example 4

This example relates to another melt transfer layer formulation, MeltTransfer Layer Formulation 4.

Melt Transfer Layer Formulation 4. Components Parts Polyurethane 100Parts (Estane ™ 5703 TPU, (Noveon ™))

Example 5

This example relates to another melt transfer layer formulation, MeltTransfer Layer Formulation 5.

Melt Transfer Layer Formulation 5 Components Parts Polyolefin-polyamideCopolymer 100 Parts (Vestamelt 432 (Degussa Co.)

Melt Transfer Layer Formulation 5 may be prepared by applying thecopolymer powder to the support under a sintering temperature of 200° C.The final dry basis weight was 20 g/m.sup.2.

Example 6

This example relates to another melt transfer layer formulation, MeltTransfer Layer Formulation 6.

Melt Transfer Layer Formulation 6 Components Parts Polyethylene Powder100 Parts (Icotex 520-5016 (Icopolymers Co.)

Melt Transfer Layer Formulation 6 may be prepared by applying thepolyethylene powder to the support under a sintering temperature of 200°C. The final dry basis weight was 20 g/m.sup.2.

Example 7

This example relates to an image receiving layer formulation, ImageReceiving Layer Formulation 1.

Image Receiving Layer Formulation 1 Components Parts Ethylene AcrylicCopolymer(Rhoplex 95 Parts NW-1402 (Rohm and Haas)) Cationic Polymer(APC-M1, Advanced 5 Parts Polymers, Inc.)

Image Receiving Layer Formulation 1 may be prepared by mixing partscationic polymer dispersion to 95 parts ethylene acrylic co-polymerdispersion by gentle stirring.

Example 8

This example relates to another image receiving layer formulation, Imagereceiving layer Formulation 2.

Image Receiving Layer Formulation 2 Components Parts Ethylene AcrylicCopolymer(Rhoplex 92 Parts NW-1402 (Rohm and Haas)) Cationic Polymer(APC-J81, Advanced 8 Parts Polymers, Inc.)

Image Receiving Layer Formulation 2 may be prepared by mixing 8 partscationic polymer dispersion to 92 parts ethylene acrylic co-polymerdispersion by gentle stirring.

Example 9

This example relates to another image receiving layer formulation, Imagereceiving Layer Formulation 3.

Image Receiving Layer Formulation 3 Components Parts Ethylene AcrylicCopolymer(Rhoplex 60 Parts NW-1402 (Rohm and Haas)) Polyethylene Wax(Michem Emulsion 37 Parts 58035, (Michelman, Inc.) Cationic Polymer(APC-J81, Advanced 3 Parts Parts Polymers, Inc.)

Image Receiving Layer Formulation 3 may be prepared by mixing 3 partscationic polymer dispersion to 60 parts ethylene acrylic co-polymerdispersion by gentle stirring. 37 parts of a polyethylene wax dispersionis then mixed into the formulation by gentle stirring.

Example 10

This example relates to another image receiving layer formulation, ImageReceiving Layer Formulation 4

Image Receiving Layer Formulation 4 Components Parts Ethylene AcrylicCopolymer(Rhoplex 60 Parts NW-1402 (Rohm and Haas)) Polyethylene Wax(Michem Emulsion 37 Parts 58035, (Michelman, Inc.) Cationic Polymer(APC-M1, Advanced 3 Parts Polymers, Inc.)

Image Receiving Layer Formulation 4 may be prepared by mixing 3 partscationic polymer dispersion to 60 parts ethylene acrylic co-polymerdispersion by gentle stirring. 37 parts of a polyethylene wax dispersionis then mixed into the formulation by gentle stirring.

Example 11

This example relates to another image receiving layer formulation, ImageReceiving Layer Formulation 5.

Image Receiving Layer Formulation 5 Components Parts Water 89 PartsCationic Polymer (APC-J81, Advanced 8 Parts Polymers, Inc.) CalciumChloride 2 Parts Polyethylene oxide) (Polyox WSR N60K 1 Part (DowChemical Co.))

Image Receiving Layer Formulation 5 may be prepared by mixing 8 partscationic polymer dispersion to 89 parts water by gentle stirring. Twoparts calcium chloride and 1 part poly(ethylene oxide) are likewisedispersed into the water solution by gentle stirring.

Example 12

This example relates to another image receiving layer formulation, ImageReceiving Layer Formulation 6.

Image Receiving Layer Formulation 6 Components Parts Ethylene AcrylicCopolymer (Michem Prime 80 Parts 4990 (Michelman, Inc.)) Wax Dispersion(Michem Emulsion 20 Parts 58035 (Michelman, Inc.)

Image Receiving Layer Formulation 6 may be prepared by mixing 20 partswax dispersion to 80 parts ethylene acrylic co-polymer dispersion bygentle stirring.

Example 13

This example relates to another image receiving layer formulation, ImageReceiving Layer Formulation 7.

Image Receiving Layer Formulation 7 Components Parts Water 83 PartsCationic Polymer (APC-J81, Advanced 8 Parts Polymers, Inc.) PolyvinylAlcohol (Celvol 540, 5 Parts Celanese Co) Calcium Chloride 2 PartsPoly(ethylene oxide) (Polyox WSR N60K 1 Part (Dow Chemical Co.)) Glyoxal(Aldrich) 1 Part

Image Receiving Layer Formulation 7 may be prepared by mixing 8 partscationic polymer dispersion to 83 parts water by gentle stirring. Fiveparts polyvinyl alcohol is then dispersed via gentle stirring andheating. Once the solution cools back to room temperature, two partscalcium chloride and 1 part poly(ethylene oxide) are likewise dispersedinto the water solution by gentle stirring. One part glyoxal is thenstirred into the mixture via gentle stirring.

Example 14

This example relates to an image receiving layer formulation, ImageReceiving Layer Formulation 8.

Image Receiving Layer Formulation 8 Components Parts Ethylene AcrylicCopolymer(Rhoplex 94 Parts B-15 (Rohm and Haas)) Cationic Polymer(APC-M1, Advanced 5 Parts Polymers, Inc.) Multifunctional AziridineCrosslinker 1 Part (XAMA-7, Sybron Co)

Image Receiving Layer Formulation 8 may be prepared by mixing 5 partscationic polymer dispersion and 1 part aziridine crosslinker to 94 partsethylene acrylic co-polymer dispersion by gentle stirring.

Example 15

This example relates to an image receiving layer formulation, ImageReceiving Layer Formulation 9.

Image Receiving Layer Formulation 9 Components Parts Ethylene vinylacetate Copolymer 60 Parts (Dur-o-set Elite Plus 25-299A (Vinamul))Polyethylene Wax (Michem Emulsion 37 Parts Fglass X9M, (Michelman, Inc.)Cationic Polymer (APC-M1, Advanced 3 Parts Polymers, Inc.)

Image Receiving Layer Formulation 9 may be prepared by mixing 3 partscationic polymer dispersion to 60 parts ethylene acrylic co-polymerdispersion by gentle stirring. 37 parts of a polyethylene wax dispersionis then mixed into the formulation by gentle stirring.

Example 16

This example relates to an image receiving layer formulation, ImageReceiving Layer Formulation 10.

Image Receiving Layer Formulation 10 Components Parts Ethylene vinylacetate Copolymer 60 Parts (Dur-o-set Elite Plus 25-299A (Vinamul))Water 37 Parts Cationic Polymer (APC-M1, Advanced 3 Parts Polymers,Inc.)

Image Receiving Layer Formulation 10 may be prepared by mixing 3 partscationic polymer dispersion to 60 parts ethylene acrylic co-polymerdispersion by gentle stirring. Thirty-seven parts of water is then addedunder gentle stirring.

Example 17

This example relates to an image receiving layer formulation, ImageReceiving Layer Formulation 11.

Image Receiving Layer Formulation 11 Parts by weight Components (DRY)Polyquaternium-10 0.15 parts (Celquat SC-230M; National Starch Co.)Self-crosslinking EVA polymer 15 Parts (Duroset Elite Plus 25-299A;Vinamul Polymers Corp.) Cationic Polymer (APC-M1; 1.8 parts AdvancedPolymer Inc.) Nylon 6-12 (Orgasol 3501 EXDNAT 1; Atofina) 8 parts EVA(Microthene FE-532; Equistar Chem. Co) 10 parts Silica (Syloid W-500;Grace Davidson) 15 parts

Image Receiving Layer Formulation 11 is displayed in dry weights.However, some of these ingredient correspond to wet amounts added tocreate the formulation. These wet amounts by weight are found below:

Parts by weight Components (WET) Polyquaternium-10 n/a (Celquat SC-230M;National Starch Co.) Self-crosslinking EVA polymer 30 (50% solids)(Duroset Elite Plus 25-299A; Vinamul Polymers Corp.) Water 70 CationicPolymer (APC-M1;  3 (60% solids) Advanced Polymer Inc.) Nylon 6-12(Orgasol 3501 EXDNAT 1; Atofina) n/a EVA (Microthene FE-532; EquistarChem. Co) n/a Silica (Syloid W-500; Grace Davidson) n/a

Example 18

This example relates to an image receiving layer formulation, ImageReceiving Layer Formulation 12.

Image Receiving Layer Formulation 12 Parts by weight Components (DRY)29% Orgasol ® 3501 EXDNAT Polyamide 9.6 Parts Resin (Atofina Chemicals,Inc. 20% EVA (Microthene FE-532; 10 Parts Equistar Chem. Co)Self-crosslinking EVA polymer 15 Parts (Duroset Elite Plus 25-299A;Vinamul Polymers Corp.) Cationic Polymer (APC-M1; 1.8 Parts AdvancedPolymer Inc.) Silica (Syloid W-500; Grace Davidson) 15 Parts Alcogum  ®L-520 (Alco Chemical) 0.6 Parts

Image Receiving Layer Formulation 12 is displayed in dry parts byweights. However, some of the above ingredients correspond to wetamounts added to create the formulation. To prepare, first two stocksolutions are prepared in water. These are as follows:

29% Orgasol 3501 EXDNAT 1 Water 100 parts Triton X-100 3 parts(surfactant) Orgasol 3501 30 parts 20% Microthene Water 100 parts TritonX-100 1 part Microthene FE-532 20 parts

These ingredients are then mixed with the other ingredients shown above.The mixing is performed wet, and the amounts in Wet parts by weight areshown below:

Parts by weight Components (WET) 29% Orgasol ® 3501 EXDNAT PolyamideResin 33 (Atofina Chemicals, Inc. 20% EVA (Microthene FE-532; EquistarChem. Co) 50 Self-crosslinking EVA polymer (Duroset Elite 30 (50%solids) Plus 25-299A; Vinamul Polymers Corp.) Cationic Polymer (APC-M1;Advanced Polymer Inc.) 3 (60% solids) Silica (Syloid W-500; GraceDavidson) n/a Alcogum .RTM. L-520 (Alco Chemical) 3 (20% solids)

Example 19

This example relates is the same as Image Receiving Layer Formulation 12of Example 18, with the exception that the parts by weight of certaincomponents are modified, the Alcogum® L-520 (Alco Chemical) is absentand Laponite, a defoamer and an antioxidant have been added.

Image Receiving Layer Formulation 13 Parts by weight Components (DRY)29% Orgasol  ® 3501 EXDNAT Polyamide Resin 9.7 Parts (Atolina Chemicals,Inc. 20% EVA (Microthene FE-S32; Equistar Chern. Co) 10 PartsSelf-crosslinking EVA polymer (Duro set Elite 20 Parts Pius 25-299A;Vinamul Polymers Corp.) Cationic Polymer (APC-M1; Advanced Polymer Inc.)2 Parts Silica (Syloid W-500; Grace Davidson) 11 Parts Laponite 0.8Parts Defoamer 0.1 Parts Antioxidant 0.5 Parts

Example 20

A transfer sheet according to the present invention is prepared asfollows:

A support layer is first coated with a barrier layer, Barrier LayerFormulation 1, below. Next, a melt transfer layer comprising aterpolymer of ethylene-vinyl acetate and maleic anhydride is extrudedonto the barrier layer. Next, an Image Receiving Layer (formulation 12)is applied via a dunk and squeeze application method.

After thermal drying, an image is formed on the side of the imagereceiving layer opposite the support material by an ink jet printer.

The transfer of the image area from the image transfer sheet iscompleted by peeling the imaged image receiving layer and melt transferlayer from the support, and placing the peeled material, image side up,on a cotton shirt. Next a non-stick sheet is placed on top of the imagedpeeled material and heat and pressure from a conventional iron set onits highest temperature setting is applied through the non-stick sheetfor a time sufficient to transfer the image area to the shirt (e.g. 3-5minutes). Lastly, the non-stick sheet is removed.

Example 21

A transfer sheet according to the present invention is prepared asfollows:

Example 20 is repeated except the melt transfer layer is applied bylamination rather than melt extrusion

Example 22

Example 17 is repeated, except that the back surface of the support(opposite the barrier layer) is coated with the following antistaticlayer:

Antistatic Layer Solution Formulation 1 Components Parts Water 90 parts(by weight) Quaternary ammonium salt solution 10 parts (by weight)(Statik-Blok J-2, Amstat Industries)

The antistatic solution is applied in a long line across the top edge ofthe support material using a #4 metering rod. The coated support isforce air dried for approximately one minute. The antistatic solution ofthis Example has the following characteristics: the solution viscosityas measured on a Brookfield DV-I+ viscometer, LV1 spindle @60 RPM is 2.0(cP) at 24.5° C. The coating weight (wet) was 15 g/m.sup.2. The surfacetension is 69.5 dynes/cm at 24° C.

Once the support and antistatic coating are dry, the uncoated side ofthe support coated with the barrier layer, melt transfer layer and imagereceiving layer.

Example 23

Example 22 is repeated, except that following formulation is used as theantistatic layer:

Antistatic Layer Solution Formulation 2 Components Parts Water 95 parts(by weight) Polyether (Marklear ALF-23, Witco Ind.) 5 parts (by weight)

Example 24

A transfer sheet according to the present invention is prepared asfollows:

A support layer is first coated with a barrier layer, Barrier LayerFormulation 1, below. Next, a melt transfer layer comprisingpolyurethane, for instance, Melt Transfer Layer Formulation 4 is appliedonto the barrier layer. Next, an Image Receiving Layer (formulation 13)is applied via a dunk and squeeze application method.

After thermal drying, an image is formed on the side of the imagereceiving layer opposite the support material by an ink jet printer.

The transfer of the image area from the image transfer sheet iscompleted by peeling the imaged image receiving layer and melt transferlayer from the support, and placing the peeled material, image side up,on a cotton shirt. Next a non-stick sheet is placed on top of the imagedpeeled material and heat and pressure from a conventional iron set onits highest temperature setting is applied through the non-stick sheetfor a time sufficient to transfer the image area to the shirt (e.g. 3-5minutes). Lastly, the non-stick sheet is removed.

Example 25

This example relates to a Barrier Layer Formulation 1:

Barrier Layer Formulation 1 Components Parts Ethylene Acrylic AcidCopolymer (Hycar 26138 100 (Noveon, Co.)

Example 26

An example of optional Opaque Layer A is as follows:

Opaque Layer A Formulation 1 Ingredient Parts Stryrene-Butadiene Latex(Latex CP 615NA, 40 Dow Chemical Co., Midland, MI) Pigment in ResinSolution 25 (Arrowvure F. Flink Ink CO., W. Hazelton, PA) ThermoplasticElastomer 17.5 (Hystretch V-29, B F Goodrich, Cleveland, OH) Elastomer17.5 (Hycar 1561, B F Goodrich, Cleveland, OH)

Example 27

An example of optional Opaque Layer B is as follows:

Opaque Layer B Formulation 1 Ingrediant Parts Vinyl Acetate-EthyleneCopolymer 35 (Airflex 124, Airproducts Inc., Allentown, PA) TiO2 PowderPigment 25 (TiPure R706, DuPont Chemicals, Wilmington, DE) ThermoplasticElastomer 25 (Hystretch V-29, B F Goodrich, Cleveland, OH) Elastomer 15(Hycar 1561, B F Goodrich, Cleveland, OH).

Example 28

A transfer sheet according to the present invention is prepared asfollows:

A support layer is first coated with Barrier Layer Formulation 1. Next,a melt transfer layer comprising polyurethane, for instance, MeltTransfer Layer Formulation 4 is applied onto the barrier layer. Next, atleast one opaque layer, for instance, Opaque Layer A Formulation 1and/or Opaque Layer B Formulation 1 is/are applied over the MeltTransfer Layer. Next, an Image Receiving Layer (formulation 13) isapplied via a dunk and squeeze application method over the Opaque Layer.

After thermal drying, the Melt Transfer Layer, Opaque Layer A and/orOpaque Layer B, and the Image Receiving Layer are peeled from thebarrier-coated support. An image is then formed on the image receivinglayer.

The transfer of the image area from the image transfer sheet is placingthe peeled material, image side up, on a cotton shirt. Next a non-sticksheet is placed on top of the imaged material and heat and pressure froma conventional iron set on its highest temperature setting is appliedthrough the non-stick sheet for a time sufficient to transfer the imagearea to the shirt (e.g. 3-5 minutes). Lastly, the non-stick sheet isremoved.

All cited patents, publications, copending applications, and provisionalapplications referred to in this application are herein incorporated byreference.

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the present invention, and allsuch modifications as would be obvious to one skilled in the art areintended to be included within the scope of the following claims.

What is claimed is:
 1. An image transfer sheet for transferring an image to a receptor element, the image transfer sheet comprising: a melt transfer layer; an image receiving layer; and a first opaque layer positioned between the melt transfer layer and the image receiving layer, the first opaque layer comprising a thermoplastic elastomer and a white pigment; and a second opaque layer positioned between the melt transfer layer and the image receiving layer, the second opaque layer comprising a thermoplastic elastomer and a white pigment; wherein the combined thickness of the first and second opaque layers is between 0.5 to 2.5 mils; and wherein the second opaque layer has a composition different from a composition of the first opaque layer.
 2. The image transfer sheet of claim 1, wherein the melt transfer layer has a thickness of between 1 to 5 mils.
 3. The image transfer sheet of claim 2, wherein the melt transfer layer comprises at least one of a polyolefin, polyester, polyurethane, and acrylic polymer, the at least one of the polyolefin, polyester, polyurethane, and acrylic polymer having a melt transition temperature in the range of 50° C. to 250° C.
 4. The image transfer sheet of claim 3, wherein the image receiving layer is formulated to retain a dye or ink image therewithin.
 5. The image transfer sheet of claim 4, wherein the image receiving layer is formulated to retain an image formed by a laser printer, laser copier, or inkjet printer.
 6. The image transfer sheet of claim 5, wherein the image receiving layer is configured to heat seal the image upon application of heat to the image transfer sheet.
 7. The image transfer sheet of claim 6, wherein the image receiving layer comprises polyurethane.
 8. The image transfer sheet of claim 7, wherein the image receiving layer further comprises a polyamide.
 9. The image transfer sheet of claim 8, further comprising a removable support adjacent the melt transfer layer.
 10. The image transfer sheet of claim 8, wherein the image transfer sheet is configured to receive an image at the image receiving layer in the absence of a support layer that does not transfer to the receptor element.
 11. The image transfer sheet of claim 10, wherein at least one of the first opaque layer and second opaque layer provide a rigid or stiff quality to the image transfer sheet such that the image receiving layer can receive the image in the absence of a support layer that does not transfer to the receptor element.
 12. The image transfer sheet of claim 6, wherein the image receiving layer comprises a cationic polymer.
 13. The image transfer sheet of claim 2, wherein the melt transfer layer comprises at least one of a polyolefin, polyester, polyurethane, and acrylic polymer, the at least one of the polyolefin, polyester, polyurethane, and acrylic polymer having a glass transition temperature (Tg) of less than 25° C.
 14. The image transfer sheet of claim 13, wherein the first opaque layer further comprises styrene-butadiene latex.
 15. The image transfer sheet of claim 13, wherein the second opaque layer further comprises vinyl acetate-ethylene.
 16. The image transfer sheet of claim 2, wherein the first opaque layer further comprises styrene-butadiene latex.
 17. The image transfer sheet of claim 2, wherein the second opaque layer further comprises vinyl acetate-ethylene. 